Examining carbonate dissolution kinetics at mineral-water interface is crucial to understand numerous environmental and geochemical processes,including global carbon cycling,CO_(2)sequestration in deep geological rese...Examining carbonate dissolution kinetics at mineral-water interface is crucial to understand numerous environmental and geochemical processes,including global carbon cycling,CO_(2)sequestration in deep geological reservoirs,and trace elements release in terrestrial and aquatic environments.Here we explored the effect of circumneutral to alkaline pH solutions(pH 6-11)on dissolution kinetics of pure dolomite and Ca and Mg release stoichiometry in flow-through reactor experiments at 25±1℃.Results revealed that the dolomite dissolution rates obtained from effluent Ca and Mg concentrations(R_(Ca)and R_(Mg)in mol/cm^(2)/s)were dependent on input solution pH and HCO_(3)^(-)log activity.The pH dependence of dissolution rates showed two distinct trends,i.e.,at circumneutral pH ranging between 6 and 8,the dissolution rate decreased with increasing pH,with minimum rate at pH 8.While in the highly alkaline pH range(pH 9-11),the dolomite dissolution rate increased with an increasing pH.Irrespective of the input pH,the dolomite dissolution rates indicated a reverse relationship with HCO_(3)^(-)log activity,with the lowest dissolution rate(R Ca=3.80×10^(-12)mol/cm^(2)/s)at pH 8 where HCO_(3)^(-)log activity attained the highest value(-3.957).The lower R Ca and R Mg obtained at pH 8 compared to all the other pH could possibly be attributed to an inhibition caused by high HCO_(3)^(-)log activity in solution at this pH.Dolomite dissolution rates were non-stoichiometric at all the experimental pH values,showing higher preferential Ca over Mg release(R_(Ca)>R_(Mg))whereas an opposite trend was observed at pH 8,with R_(Ca)<R_(Mg)at the steady state.Saturation index values calculated using geochemical speciation modelling were positive for Mg-bearing minerals(brucite,dolomite,artinite)at alkaline pH of 10-11,indicating favourable conditions for their precipitation under studied conditions.This study provides insights on the significance of log ion activities of HCO_(3)^(-)and Me-OH^(+)under varying pH for elucidating the dissolution mechanism of dolomite in circumneutral to alkaline aqueous environments.展开更多
基金funding enabled and organized by CAUL and its Member Institutionsby COMSTEQ-TWAS research grant 2018(18-268 RG/EAS/AS_C)。
文摘Examining carbonate dissolution kinetics at mineral-water interface is crucial to understand numerous environmental and geochemical processes,including global carbon cycling,CO_(2)sequestration in deep geological reservoirs,and trace elements release in terrestrial and aquatic environments.Here we explored the effect of circumneutral to alkaline pH solutions(pH 6-11)on dissolution kinetics of pure dolomite and Ca and Mg release stoichiometry in flow-through reactor experiments at 25±1℃.Results revealed that the dolomite dissolution rates obtained from effluent Ca and Mg concentrations(R_(Ca)and R_(Mg)in mol/cm^(2)/s)were dependent on input solution pH and HCO_(3)^(-)log activity.The pH dependence of dissolution rates showed two distinct trends,i.e.,at circumneutral pH ranging between 6 and 8,the dissolution rate decreased with increasing pH,with minimum rate at pH 8.While in the highly alkaline pH range(pH 9-11),the dolomite dissolution rate increased with an increasing pH.Irrespective of the input pH,the dolomite dissolution rates indicated a reverse relationship with HCO_(3)^(-)log activity,with the lowest dissolution rate(R Ca=3.80×10^(-12)mol/cm^(2)/s)at pH 8 where HCO_(3)^(-)log activity attained the highest value(-3.957).The lower R Ca and R Mg obtained at pH 8 compared to all the other pH could possibly be attributed to an inhibition caused by high HCO_(3)^(-)log activity in solution at this pH.Dolomite dissolution rates were non-stoichiometric at all the experimental pH values,showing higher preferential Ca over Mg release(R_(Ca)>R_(Mg))whereas an opposite trend was observed at pH 8,with R_(Ca)<R_(Mg)at the steady state.Saturation index values calculated using geochemical speciation modelling were positive for Mg-bearing minerals(brucite,dolomite,artinite)at alkaline pH of 10-11,indicating favourable conditions for their precipitation under studied conditions.This study provides insights on the significance of log ion activities of HCO_(3)^(-)and Me-OH^(+)under varying pH for elucidating the dissolution mechanism of dolomite in circumneutral to alkaline aqueous environments.
